TWI409287B - Curable resin composition, curable film and their cured products - Google Patents

Abstract

A curable resin composition containing a specific vinyl compound obtained by vinylation of a terminal of a bifunctional phenylene ether oligomer having a polyphenylene ether structure in a molecule and a specific bismaleimide compound having at least two maleimide groups in a molecule, a curable film comprising the above composition, a cured product obtained by curing the above composition, and a film obtained by curing the curable film. The above resin composition is excellent in curability even in the presence of oxygen, is curable at a low temperature and is capable of giving a cured product having a low dielectric constant, a low dielectric loss tangent, high heat resistance, excellent mechanical properties, excellent chemical resistance and excellent flame retardancy.

Description

Curable resin composition, curable film, and the like

The present invention relates to a curable resin composition which can be cured in the presence of oxygen or at a low temperature and which can produce a cured product having excellent low dielectric properties, heat resistance, mechanical properties and chemical resistance, and is composed by hardening the above resin Each of the hardened materials using the resin composition and a curable film or film were obtained. The curable resin composition, curable film, cured product, and film of the present invention are suitable for use in the field of electronic materials, such as resins for printed wiring boards, sealing resins for semiconductors, interlayer insulating materials for semiconductors, and the like. Insulation material for electronic components.

Conventional curable resins are widely used in bonding, casting, coating, dipping, laminating, molding compounds, and the like. However, curable resins are used in so many fields that conventional hardening resins are unsatisfactory under certain use environments or under certain use conditions.

In the field of information communication and computers, for example, the signal band of an information communication device such as a PHS or a mobile phone and the CPU clock time of a computer reach the GHz band. In order to control the damping due to the electrical signals of the insulator, the insulator requires a material having a low dielectric constant and a low dielectric loss tangent. These materials are recommended to be a fluorine-containing resin, a polyolefin resin, a polystyrene resin, a polyphenylene ether resin, and a vinyl benzyl ether resin (for example, see JP-A-7-188362, JP-A-2004- 83680, Japanese Patent No. 3414556 and JP-A-2003-306591).

However, although these materials have excellent dielectric properties, they are not necessarily It satisfies all the physical properties required for electronic components other than dielectric properties, such as heat resistance, chemical resistance, and mechanical properties.

In the field of printed wiring boards and semiconductor packages, for example, due to the recently adopted lead-free solder, the temperature at the time of soldering is increased. In order to ensure higher mounting reliability, constituent materials of printed wiring boards, semiconductor packages, and electronic components are required to have high heat resistance, low water absorption, low thermal expansion, and the like. For the hardening step of the curable resin used for these materials, an increase in productivity, such as curing in an oven in the presence of oxygen and hardening at a low temperature, is strongly required. In addition, flame retardancy is often necessary for electronic components from the standpoint of product safety.

The present inventors have developed a vinyl compound derivative of a bifunctional phenylene ether oligomer and a derivative containing the same for the purpose of satisfying the above requirements of low dielectric properties, heat resistance, chemical resistance, and low water absorption. A curable resin composition (for example, see JP-A-2004-59644 and JP-A-2006-83364). The above-mentioned derivative and the above-mentioned curable resin composition are hardened under conditions of curing, which are not often in contact with oxygen, for example, a stamper in which a resin composition is placed in a mold, or a hardening of a gas phase in a inert oven. Has excellent hardening properties. Under these conditions, the cured product can obtain excellent low dielectric properties, heat resistance, and mechanical properties. However, for example, when the derivative and the above-mentioned curable resin composition are in the form of a coating film or film in the case where they are often in contact with oxygen, when they are hardened by using an air gas oven, they are not sufficiently hardened, and therefore, it is necessary to carry out Improve. Even when it is used for hardening in a state in which it is not often in contact with oxygen, for example, under nitrogen, under reduced pressure, or under pressure, in order to increase productivity, A material that can be hardened at a low temperature is desired.

An object of the present invention is to provide a curable resin composition which produces a low dielectric constant, a low dielectric loss tangent, excellent heat resistance, excellent mechanical properties, excellent chemical resistance, and excellent flame retardancy. And a cured product which is excellent in hardenability in the presence of oxygen, and which can be cured at a low pressure, a hardenable film containing the above composition, a cured product obtained by hardening the above composition, and a hardened film form by curing the above composition The film obtained.

The present inventors conducted diligent research to achieve the above object, and the results are listed later. When a vinyl-terminated compound having a polyfunctional phenylene ether oligomer having a polyphenylene ether structure in the molecule is combined with a bismaleimide compound having a specific structure, even in the presence of oxygen, the resulting composition It is hardenable, which lowers the hardening temperature, and the cured product obtained therefrom has a low dielectric constant, a low dielectric loss tangent, a high glass transition temperature (Tg), high strength, and excellent chemical resistance. Based on the above findings, the inventors completed the present invention.

That is, the present invention relates to a curable resin composition comprising, as a main component, a vinyl compound (a) represented by the general formula (1) and a male quinone represented by the general formulae (5) to (8). a maleimide compound (b) of the imine compound (b) or at least two maleimide compounds (b), provided that the curable resin composition may comprise at least two formulas different in structure from each other ( 1) A mixture of compounds (a). The present invention relates to further comprising at least one selected from the group consisting of styrene thermoplastic elastomer (c), flame retardant (d) Or a component of the filler (e) is incorporated into the curable resin composition obtained by the above curable resin composition.

Wherein -(OXO)- represents a moiety of the formula (2) or the formula (3), -(YO)- represents an arrangement of a moiety of the formula (4) or a random arrangement of at least two moieties of the formula (4) And each of a and b is an integer from 0 to 100, but at least one of a and b is not zero.

Wherein R ₁ , R ₂ , R ₃ , R ₇ and R ₈ are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R ₄ , R ₅ and R ₆ are the same Or different, and represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group.

Wherein R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or benzene The group -A- represents a linear, branched or cyclic divalent hydrocarbon group having 20 or fewer carbon atoms.

Wherein R ₁₇ and R ₁₈ are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R ₁₉ and R ₂₀ are the same or different and represent a hydrogen atom, a halogen atom, or An alkyl group or a phenyl group of 6 or less carbon atoms.

Wherein R ₂₁ to R ₂₈ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, and B represents a single bond, a divalent hydrocarbon group having 20 or less carbon atoms or an oxygen atom.

Wherein R ₂₉ to R ₃₆ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, and D represents a divalent hydrocarbon group having 20 or less carbon atoms.

Wherein R ₃₇ to R ₄₇ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, and c is an integer of 1 to 20.

Wherein E represents a divalent aliphatic hydrocarbon group having 20 or less carbon atoms.

Further, the present invention relates to a cured product obtained by curing the above resin composition, a curable film obtained by processing the above resin composition into a film form, and a hardened film obtained by hardening the above resin composition into a film form. film.

(Effect of the invention)

Since the curable resin composition of the present invention is used, it can be hardened in the presence of oxygen. Therefore, in particular, a cured product in the form of a coating film or a film can be easily obtained. In addition, since the hardening temperature can be lowered, the productivity is improved. The cured product obtained from the resin composition of the present invention has excellent low dielectric properties, high heat resistance, chemical resistance and mechanical properties, and therefore it is expected that the resin composition of the present invention can be used for insulating materials of high frequency electronic components and insulating materials for semiconductors. Material of circuit board add-on, material of copper clad laminate, coating material, coating, adhesive, film of capacitor, die connection film, cover film, conductive paste, solder mask, flexible circuit board Materials, fiber reinforced plastics, and more. Therefore, its industrial significance is very high.

The vinyl compound (a) used in the curable resin composition of the present invention represented by the general formula (1) is not particularly limited as long as it is a vinyl compound represented by the general formula (1), wherein -(OXO) a portion representing the formula (2), and wherein R ₁ , R ₂ , R ₃ , R ₇ and R ₈ are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a benzene The group, R ₄ , R ₅ and R ₆ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; or a moiety of the formula (3), and wherein R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, -A- represents a moiety having a linear, branched or cyclic divalent hydrocarbon group of 20 or less carbon atoms; -(YO)- represents an arrangement of moieties of the formula (4) or at least two formulas (4) The portions are randomly arranged, and wherein R ₁₇ and R ₁₈ are the same or different and represent a halogen atom, an alkyl group having 6 or fewer carbon atoms or a phenyl group, and R ₁₉ and R ₂₀ are the same or different and represent A hydrogen atom a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and each of a and b is an integer of 0 to 100, but at least one of a and b is not 0. Further, at least two vinyl compounds (a) having different structures may be contained in the curable resin composition.

Examples of -A- in the general formula (3) include divalent hydrocarbon groups such as methylene, ethylene, 1-methylethylene, 1, 1-propylene, and 1,4-phenylene bis ( 1-methylethylidene), 1, 3-phenylenebis(1-methylethylidene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene base. -A- in the general formula (3) is not limited to these examples.

The vinyl compound (a) in the present invention is preferably a vinyl compound (a) wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ and R ₁₈ have 3 or less carbon atoms. An alkyl group, and R ₄ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ and R ₂₀ are a hydrogen atom or have 3 or An alkyl group having fewer carbon atoms, particularly preferably a vinyl compound (a) wherein -(OXO)- represented by the general formula (2) or the general formula (3) is a general formula (9) or a general formula (10) Or a moiety of the formula (11), and -(YO)- represented by the formula (4) is an arrangement of a moiety of the formula (12), an arrangement of a moiety of the formula (13) or a formula (12) and A random arrangement of the parts of the formula (13).

Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same or different and represent a hydrogen atom or a methyl group, and -A- represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Wherein -A- represents a linear, branched or cyclic divalent hydrocarbon group having 20 or fewer carbon atoms.

The molecular weight of the vinyl compound (a) preferably has a number average molecular weight of 500 to 3,000, and the molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably in the range of 1 to 3. When the number average molecular weight is less than 500, the coating film of the curable resin composition is liable to be sticky. When the number average molecular weight exceeds 3,000, the solubility of the resin composition in the solvent is lowered. When the molecular weight distribution exceeds 3, in some cases, the solubility of the curable resin composition in a solvent is poor and the hardening of the curable resin composition is vitrified. The transfer temperature is lowered. The method for producing the vinyl compound (a) is not particularly limited. For example, a terminal phenolic hydroxyl group of a difunctional phenylene ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound is etherified with a vinyl benzyl group to produce a vinyl compound (a).

For example, a bifunctional phenol compound, a monofunctional phenol compound, and a catalyst are dissolved in a solvent and then oxygen is added to the resulting solution under heating and stirring to obtain a difunctional phenylene ether oligomer.

Examples of the bifunctional phenol compound include 2, 2', 3, 3', 5, 5'-hexamethyl-(1, 1'-diphenyl)-4, 4'-diol, 4, 4'- Methylene bis(2,6-dimethylphenol), 4,4'-dihydroxyphenylmethane and 2,2-bis(4-hydroxyphenyl)propane. The bifunctional phenol compound is not limited to these examples.

The monofunctional phenol compound is usually 2,6-dimethylphenol or 2,3,6-trimethylphenol. The monofunctional phenol compound is not limited to these examples.

The catalyst is, for example, a combination of a copper salt and an amine. Examples of copper salts include CuCl, CuBr, CuI, CuCl ₂ and CuBr ₂ . Examples of amines include di-n-butylamine, n-butyldimethylamine, N,N'-di-t-butylethylenediamine, N,N,N',N'-tetramethylethylenediamine, pyridine, and piperazine. Pyridine and imidazole. The catalyst is not limited to these examples.

Examples of the solvent include toluene, methanol, methyl ethyl ketone, and xylene. The solvent is not limited to these examples.

A method of vinylbenzyl etherification of a terminal phenolic hydroxyl group of a difunctional phenylene ether oligomer, for example, a difunctional phenylene ether oligomer and a vinylbenzyl chloride can be dissolved in a solvent to obtain a solution Adding a base to the solution under heating and stirring to react the components and then curing the resin to carry out the growth Production.

Vinylbenzyl chloride includes o-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl chloride, and mixtures thereof.

Examples of the base include sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide.

The base is not limited to these examples.

The base remaining after the reaction can be neutralized with an acid. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid. The acid is not limited to these examples.

Examples of the solvent used for the reaction include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, dichloromethane, and chloroform. The solvent used for the reaction is not limited to these examples.

As a method of curing, there are a method of curing in which drying by evaporation of a solvent and a method in which a reaction liquid is mixed with a poor solvent to precipitate a solid. It is not limited to these methods.

The maleic imine compound (b) used in the curable resin composition of the present invention is not particularly limited as long as it is selected from the maleimide compounds represented by the general formulae (5) to (8), wherein R ₂₁ to R ₄₇ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, B represents a single bond, a divalent hydrocarbon group having 20 or less carbon atoms or an oxygen atom, and D represents A divalent hydrocarbon group of 20 or less carbon atoms, E represents a divalent aliphatic hydrocarbon group having 20 or less carbon atoms, and c is an integer of 1 to 20. Preferably, in the general formulae (5) to (8), R ₂₁ to R ₃₆ are the same or different and represent a hydrogen atom, an ethyl group or a methyl group, R ₃₇ to R ₄₇ represent a hydrogen atom and E represents 10 Or an aliphatic hydrocarbon group having fewer carbon atoms.

Examples of the divalent hydrocarbon group of -B- as in the formula (5) include methylene and ethylene 1, 1-methylethylene, 1, 1-propylene, 1, 4-phenylene bis(1-methylethylidene), 1, 3-phenylene bis(1-methyl Ethyl), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenylethylene, 1,3-phenylene and 1,4-phenylene. It is not limited to these examples.

Examples of -D- in the formula (6) include 1-methylethylenedi(-4,1-phenylene), methylenebis(-4,1-phenylene), 1, 3- Phenylene and 1,4-phenylene. It is not limited to these examples.

Examples of -E- in the formula (8) include ethylene, 1,4-butene, 1,6-hexene, and 2,2,4-trimethyl-1,6-hexene. It is not limited to these examples.

The maleic imine compound (b) can be used alone. Further, two or more of the maleimide compounds (b) may be used in combination.

Examples of the styrene thermoplastic elastomer (c) used in the curable resin composition of the present invention include styrene butadiene styrene copolymer (SBS), hydrogenated styrene butadiene styrene copolymer (SEBS), and benzene. Ethylene isoprene styrene copolymer (SIS), hydrogenated styrene isoprene styrene copolymer, styrene (butadiene / isoprene) styrene copolymer and hydrogenated styrene (butadiene / Isoprene) styrene copolymer. Among them, hydrogenated styrene butadiene styrene copolymer (SEBS), hydrogenated styrene isoprene styrene copolymer or hydrogenated styrene (butadiene/isoprene) styrene copolymer is preferably used because A cured product having a high glass transition temperature can be obtained and heat resistance is improved.

The content of styrene in the styrene thermoplastic elastomer (c) is not particularly limited. In order to obtain a cured product having higher heat resistance, the styrene content is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight. In addition, styrene heat The weight average molecular weight of the plastic elastomer (c) is preferably from 10,000 to 300,000. When it is too small, the coating film of the cured product may be cracked in some cases. When it is too large, it becomes difficult to mix the styrene thermoplastic elastomer (c) with the vinyl compound (a) or the maleimide compound (b).

The mixing ratio of the vinyl compound (a) and the maleimide compound (b) in the curable resin composition of the present invention is not particularly limited. When the amount of the vinyl compound (a) or the maleimide compound (b) is too large, it is difficult to obtain desired hardenability. Therefore, the vinyl group of the vinyl compound (a) and the maleimide group of the maleimide compound (b) are preferably from 1:0.1 to 1:5 (vinyl: maleimide) Base), more preferably 1:0.5 to 1:2.

The amount of the styrene thermoplastic elastomer (c) contained in the curable resin composition of the present invention is not particularly limited. When the amount is too large, the desired hardenability cannot be obtained. Therefore, (vinyl compound (a) + maleimide compound (b)): the weight of the elastomer (c) is preferably from 100:0 to 30:70, more preferably from 100:0 to 50:50.

The flame retardant (d) used in the present invention is selected from known flame retardants. Examples of the flame retardant (d) include: a halogen flame retardant such as a brominated epoxy resin, a brominated polycarbonate, a brominated polystyrene, a brominated styrene, a phthalimide bromide, and four Bromobisphenol A, pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorination Polystyrene and chlorinated paraffin; phosphorus flame retardant, such as red phosphorus, tris (toluene phosphate), triphenyl phosphate, toluene phthalate, biphenyl phosphate, trialkyl phosphate, phosphoric acid Alkyl ester, tris(phosphoric acid) Ethyl)ester, phosphazene, 1,3-phenylenebis(2,6-dixylphosphonic acid) ester and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10- Phosphenephenanthrene phosphate-10; inorganic flame retardant, such as aluminum hydroxide, magnesium hydroxide, heat-treated aluminum hydroxide obtained by heat-treating aluminum hydroxide and reducing partially crystal water, bauxite, zinc borate and antimony trioxide And organic antimony flame retardants, such as silicone rubber and organic resin. These flame retardants can be used singly or in combination. Among them, 1,3-phenylenebis(2,6-dixylphosphonic acid) ester is preferred because it does not impair low dielectric properties. The content of phosphorus in the resin composition is preferably from 0.1 to 5% by weight.

The filler (e) used in the present invention is selected from known fillers. Examples of the filler (e) include fibrous fillers such as glass fibers, carbon fibers, aramid fibers, tantalum carbide fibers, alumina fibers, boron fibers, and liquid crystalline polyester fibers; inorganic needle-shaped single crystals such as tantalum carbide, tantalum nitride , magnesium oxide, potassium titanate and boroalumino acid; inorganic acicular fibers, such as asbestos, sillimanite, phosphate fiber and sepiolite; inorganic fillers, such as vermiculite powder, fused vermiculite, talc, Alumina, barium titanate, mica, glass microbeads, barium sulfate and glass frit; organic fillers such as particulate polymers obtained by crosslinking of (meth) acrylate, styrene, etc.; and carbon black. These fillers can be used singly or in combination. The filler (e) can lower the coefficient of thermal expansion of the curable resin composition. In particular, vermiculite is preferred because it can reduce the coefficient of thermal expansion without greatly impairing low dielectric properties. The amount of the filler (e) in the resin composition is preferably from 0.1 to 80% by weight, more preferably from 10 to 70% by weight, because the strength of the coating film is lowered when it is too large.

The method of mixing the curable resin composition of the present invention is not particularly limited set. For example, there are a vinyl compound (a), a maleimide compound (b), a styrene thermoplastic elastomer (c), a flame retardant (d), and a filler (e) dissolved and dispersed in a solvent to obtain a mixture, and then a method of removing the solvent from the mixture by drying, and a vinyl compound (a), a maleimide compound (b), a styrene thermoplastic elastomer (c) using a kneader such as a Labplast mill ), a method in which the flame retardant (d) and the filler (e) are mixed.

The curable resin composition of the present invention itself is hardened by heating even in the presence of oxygen. In order to further accelerate the hardening speed and thus improve workability and economic efficiency, a thermosetting catalyst may be added. As the thermosetting catalyst, it can be used by using a substance which generates a cationic or radical active species by heating or photoinitiating vinyl polymerization. Examples of the cationic polymerization initiator include a diallyl iodonium salt, a triallyl sulfonium salt, and an aliphatic sulfonium salt each using BF ₄ , PF ₆ , AsF ₆ or SbF ₆ as a counter anion. A commercially available product can be used. Examples thereof include SP70, SP172, and CP66 supplied by ADEKA KK, CI2855 and CI2823 supplied by Nippon Soda Co., Ltd., and SI100L and SI150L supplied by Sanshin Chemical Industry Co., Ltd. The radical polymerization initiator includes: a benzoin compound such as benzoin and benzoin methyl; an acetophenone compound such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone; Thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone; bi-azido compounds such as 4-4'-diazide-chalcone, 2,6-double ( 4'-azidobenzylidene)cyclohexanone and 4-4'-bisazidobenzophenone; azo compounds such as azobisisobutyronitrile, 2,2-azobispropane and hydrazine; And organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butyl) Oxygen)hexane-3 and dicumyl peroxide. These hardening catalysts can be used singly or in combination.

A polymerization inhibitor may also be added to the curable resin composition of the present invention to improve storage stability. The polymerization inhibitor can be selected from known polymerization inhibitors. Examples thereof include anthracene such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil and trimethylhydrazine, and aromatic diol. These polymerization inhibitors can be used singly or in combination.

The curable resin composition of the present invention may contain known coupling agents, thermosetting resins, thermoplastic resins, photohardening resins, dyes, pigments, thickeners, lubricants, defoamers, ultraviolet rays required for adjusting physical properties. Absorbent, and so on.

Examples of coupling agents include decane coupling agents such as vinyl trichloromethane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, β ( 3, 4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, N-β(aminoethyl)γ-aminopropylmethylmethoxy Basear, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, and γ-chloropropyltrimethoxydecane, titanium An acid ester coupling agent, an aluminum coupling agent, a zirconium aluminate coupling agent, an organic rhodium coupling agent, and a fluorine coupling agent. These coupling agents can be used singly or in combination.

Examples of thermosetting resins include: epoxy resins such as bisphenol A type epoxy, bisphenol F type epoxy, phenol novolak type epoxy, cresol novolac type epoxy, and dicyclopentadiene. Novolak type epoxy; (meth) acrylate, such as bisphenol A type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, trimethylolpropane tri (methyl) Acrylate and bis-erythritol hexa(meth) acrylate; vinyl compounds such as divinyl benzene, divinyl naphthalene, divinyl benzene polymer, divinyl naphthalene polymer and hexamethyl bisphenol Vinyl benzyl ether; allyl compound, such as triallyl cyanurate, triallyl isocyanurate, allyl modified bisphenol A, and allyl modified polyphenylene Ether; cyanate resin, such as bisphenol A dicyanate, tetramethyl bisphenol F dicyanate, bisphenol M dicyanate and phenol novolac cyanate; oxetane resin; benzene And cyclobutene resin and benzo Resin. These thermosetting resins can be used singly or in combination.

Examples of the thermoplastic resin include polyamidimide, polyimine, polybutadiene, polyethylene, polystyrene, polycarbonate, phenoxy resin, polyisoprene, polyester, polyvinyl Butyral and polybutadiene.

The curable resin composition solution obtainable by the present invention will be explained below. The curable resin composition solution of the present invention can be obtained by dissolving and dispersing the curable resin composition of the present invention in a solvent.

Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, cyclohexane, benzene, toluene, xylene, tetrahydrofuran. ,two Alkane, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, dichloromethane, chloroform, 1, 2-Dichloroethane, ethyl acetate, butyl acetate and γ-butyrolactone. The solvent is not limited to these examples. These solvents may be used singly or in combination.

The method of dissolving is, for example, a method in which a curable resin composition and a solvent are heated and stirred in a vessel containing a stirrer. The dissolution method is not limited to the above method. The heating temperature is preferably from 30 ° C to 100 ° C.

The curable resin composition solution of the present invention is used to obtain a curable resin composition by drying the solvent. Further, the curable resin composition solution of the present invention is practical because it can be used for a resist, a prepreg or the like.

For example, a prepreg is obtained by impregnating a glass cloth, an aramid nonwoven fabric, a liquid crystalline polyester nonwoven fabric or the like with a solution of the curable resin composition of the present invention in a solvent and drying the solvent to remove the solvent. . The above prepreg can be used as a material for a copper clad laminate. Further, when a solution of the curable resin composition of the present invention in a solvent is applied onto a substrate in which a circuit has been produced, it can be used as a solder resist film or an interlayer insulating layer of a wiring board member.

The cured product of the present invention can be obtained by hardening the curable resin composition of the present invention. As a method of hardening, for example, a method in which a resin composition is heated in a mold, in which a solution of a resin composition is applied to a base material such as a glass plate, a SUS (矽 unidirectional switch) plate, or an FRP (fiber reinforced plastic) A method of removing a solvent by drying and then heating using an oven, and a method in which the solid resin composition is melted without using a solvent, the molten resin composition is cast in a mold, and heated. Although the curable resin composition of the present invention can be cured in the presence of oxygen, it is also possible to apply pressure or use an inert gas such as nitrogen or argon as the hardening gas if necessary.

The hardening temperature is preferably from 100 to 250 ° C, and the hardening period is preferably from 0.1 to 5 hours.

Further, a photopolymerization initiator may be incorporated into the resin composition of the present invention, and the resulting resin composition is cured by ultraviolet irradiation as needed. Examples of the photopolymerization initiator include: α-diketones such as benzyl and diacetamidine; acetoin ethers such as benzhydryl ether and benzhydryl isopropyl ether; thioxanthone such as thioxanthone, 2 , 4-diethylthioxanthone and 2-isopropylthioxanthone; benzophenones such as benzophenone and 4,4'-bis(dimethylamino)benzophenone; acetophenone, such as benzene Ethyl ketone, 2, 2'-dimethoxy-2-phenylacetophenone and β-methoxyacetophenone; and aminoacetophenone, such as 2-methyl-1-[4-(methyl sulfide) Phenyl]-2-morpholinylpropan-1-one and 2-benzyl-2-dimethylamino-1-(-4-morpholinylphenyl)-butanone-1.

Next, the curable resin composition of the additional base material obtainable according to the present invention will be explained. The curable resin composition of the additional base material of the present invention is obtained by applying the curable resin composition of the present invention to a base material. Examples of the base material include an organic film base material such as a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release agent applied to the film surface Release film and polyimide film obtained; conductive foil such as copper foil and aluminum foil; plate-like base material such as glass plate, SUS plate and FRP. As a coating method, for example, in which the curable resin composition of the present invention is dissolved in a solvent, a wire bar coater, a die coater, a doctor blade, a baker coater or the like is used. The solution is applied to the base material and dried to remove the solvent.

The drying conditions by drying to remove the solvent are not particularly limited. When a low temperature is employed, the solvent is liable to remain in the curable resin composition of the additional base material. When high temperature is employed, the hardening of the resin composition advances. Therefore, the drying is preferably carried out at a temperature of from 20 ° C to 150 ° C for from 1 to 90 minutes. The thickness of the resin layer can be adjusted by the concentration of the resin composition solution and the coating thickness of the resin composition. When the thickness of the coating is too thick, the solvent is liable to remain in the dry period. Therefore, the thickness is preferably from 0.1 to 500 μm.

The curable resin composition of the additional base material of the present invention can be used as an insulating layer of a printed wiring board or a material of a semiconductor package. For example, a solution of the curable resin composition of the present invention in a solvent is applied to a copper foil used as a base material, and then the coating solution is dried to obtain a copper foil of an additional resin. A solution of the curable resin composition of the present invention in a solvent is applied to a separable plastic film used as a base material, and then the coating solution is dried to obtain a film for reinforcement, a dry film solder mask or a die attach film ( Die attach film). It can be dried by heating at a temperature of 20 ° C to 150 ° C for 1 to 90 minutes and the solvent is removed. Further, the curable resin composition can be used in a non-hardened state only after the solvent is removed. Further, a semi-curable resin composition may be used as needed, and a semi-curable resin composition may be used.

The curable film of the present invention is obtained by removing the base material from the curable resin composition of the additional base material of the present invention. The method of removing the base material is usually etching or stripping.

The above curable film can be used, for example, as a mucosa.

According to the invention, a cured product of an additional base material is obtained. By hardening The hardenable resin composition of the base material is obtained to obtain a cured product of the additional base material of the present invention. The curable resin composition of the additional base material of the present invention is sufficiently hardened even in the presence of oxygen. The hardening conditions vary depending on the presence or absence of the use of the polymerization initiator and the combined use of the presence or absence of other thermosetting resins. The temperature for hardening is preferably from 100 to 250 °C. The hardening period is preferably from 0.1 to 5 hours. Further, if necessary, pressure may be applied or an inert gas such as nitrogen or argon may be used as the hardening gas. The method of heating is selected from known methods such as oven or compression.

When a copper foil is used as the base material, the cured product of the additional base material of the present invention can be used, for example, as a flexible printed wiring board material.

The film of the present invention is obtained by a method of removing the base material from the cured product of the additional base material obtained by hardening the curable resin composition of the additional base material of the present invention, curing the curable film of the present invention under heating or other methods. As a method of removing the base material, for example, etching or peeling is used. The curable film of the present invention is sufficiently hardened even in the presence of oxygen. The hardening conditions vary depending on the presence or absence of the use of the polymerization initiator and the combined use of the presence or absence of other thermosetting resins. The hardening temperature is preferably from 100 to 250 °C. The hardening period is preferably from 0.1 to 5 hours. Further, if necessary, pressure may be applied or an inert gas such as nitrogen or argon may be used as the hardening gas. The method of heating is selected from known methods such as oven or compression.

The film of the present invention can be used as, for example, a film for a capacitor.

(Example)

The present invention will be specifically described with reference to the following examples and comparative examples, however, The invention should not be limited to these embodiments. The measurement method is as follows: 1) The number average molecular weight and the weight average molecular weight are obtained by gel permeation chromatography (GPC). Data processing was performed based on the GPC curve and molecular weight calibration curve of the sample. The relationship between the molecular weight of the standard polystyrene and the elution time is approximated to obtain a molecular weight calibration curve having the following formula.

LogM=A ₀ X ³ +A ₁ X ² +A ₂ X+A ₃ +A ₄ /X ²

Wherein M: molecular weight, X: elution time -19 (minutes), and A: coefficient.

2) Determination of hydroxyl equivalent by solution absorption at 3,600 cm ^-1 by IR (infrared spectroscopy) analysis (solution cell method; cell thickness = 1 mm), wherein 2,6-dimethylphenol was used as a standard reference material, drying two Methyl chloride is used as a solvent.

3) The vinyl equivalent (solution pool method; cell thickness = 1 mm) was determined from the absorption intensity at 910 cm ^-1 in the IR analysis, in which 1-octene was used as a standard reference material and carbon disulfide was used as a solvent.

4) The glass transition temperature (Tg) was measured according to the TMA (thermo-mechanical analysis) stretching method under a load of 2.5 g, a chuck pitch of 10 mm, and a heating rate of 10 ° C / minute. The sample width is 3 mm.

5) Regarding the dielectric constant and the dielectric loss tangent, the film was rolled up in a cylindrical shape and then the values of the dielectric constant and the dielectric loss tangent were measured by a cavity resonance perturbation method at 10 GHz.

6) The breaking strength was measured in accordance with JIS K-7127. The sample type is 1B.

The test speed is 100 mm/min. Calculate the stress during the break period.

7) Regarding chemical resistance, the hardened film was immersed in tetrahydrofuran (THF) at 25 ° C for 1 hour and then it was observed whether or not dissolution occurred. (〇: not dissolved, ×: dissolved solution).

8) Regarding the flame retardancy, the film was rolled up in a cylindrical shape and then tested in accordance with the UL-94 standard thin material vertical ignition point measurement.

9) Regarding the coefficient of thermal expansion, the measurement was carried out according to the TMA stretching method at a load of 2.5 g, a chuck pitch of 10 mm, and a heating rate of 10 ° C / minute.

The average coefficient of thermal expansion from 50 to 100 ° C was calculated. The sample width is 3 mm.

(Synthesis Example 1) (Synthesis of difunctional phenylene ether oligomers)

3.88 g (17.4 mmol) of CuBr ₂ , 0.75 g (4.4 mmol) of N,N'-di-t-butylethylenediamine, 28.04 g (277.6 mmol) of n-butyldimethylamine and 2,600 g of toluene were added to have 12 liters A longitudinally long reactor of volume and equipped with a stirrer, thermometer, air sample tube and baffle. The mixture was stirred at a reaction temperature of 40 °C. 129.32 g (0.48 mol) 2, 2',3,3',5,5'-hexamethyl-(1,1'-diphenyl)-4,4'-diol, 292.19 g (2.40 mol) 2,6-Dimethylphenol, 0.51 g (2.9 mmol) of N,N'-di-t-butylethylenediamine and 10.90 g (108.0 mmol) of n-butyldimethylamine are separately dissolved in 2,300 g of methanol To obtain a mixed solution. When aeration and stirring were carried out using a nitrogen-air mixture having an 8% oxygen concentration at a flow rate of 5.2 L/min, the mixed solution was dropwise added to the mixture in the reactor over 230 minutes. After the addition was completed, 1,500 g of water in which 19.89 g (52.3 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirring mixture to terminate the reaction. The aqueous layer and the organic layer are separated. Subsequently, the organic layer was washed with a 1N aqueous solution of hydrochloric acid and then washed with purified water. The solution thus obtained was concentrated to 50% by weight using an evaporator to obtain a toluene solution of 833.40 g of a difunctional phenylene ether oligomer (resin "A"). The resin "A" had a number average molecular weight of 930, a weight average molecular weight of 1,460, and a hydroxyl equivalent of 465.

(Synthesis of vinyl compounds)

833.40 g of a toluene solution of the resin "A", 160.80 g of vinylbenzyl chloride (trade name: CMS-P; supplied by Seimi Chemical Co., Ltd.), 1,600 g of dichloromethane, 12.95 g of benzyl dimethyl Amine, 420 g of pure water and 175.9 g of a 30.5 wt% aqueous NaOH solution were added to the reactor equipped with a stirrer, a thermometer and a reflux tube. The mixture was stirred at a reaction temperature of 40 °C. The mixture was stirred for 24 hours, and then the organic layer was washed with 1N aqueous hydrochloric acid and then washed with purified water. The solution thus obtained was concentrated using an evaporator. The concentrated solution was dropped into methanol to obtain a solid. The solid was recovered by filtration and dried in vacuo to yield 501.43 g of the compound "B". The vinyl compound "B" had a number average molecular weight of 1,165, a weight average molecular weight of 1,630, and a vinyl equivalent of 595 g/vinyl group.

(Synthesis Example 2) (Synthesis of difunctional phenylene ether oligomers)

Add 9.36 g (42.1 mmol) of CuBr ₂ , 1.81 g (10.5 mmol) of N,N'-di-t-butylethylenediamine, 67.77 g (671.0 mmol) of n-butyldimethylamine and 2,600 g of toluene with 12 liters A longitudinally long reactor of volume and equipped with a stirrer, thermometer, air sample tube and baffle. The mixture was stirred at a reaction temperature of 40 °C. 129.32 g (0.48 mol) 2, 2',3,3',5,5'-hexamethyl-(1,1'-diphenyl)-4,4'-diol, 878.4 g (7.2 mol 2,6-Dimethylphenol, 1.22 g (7.2 mmol) of N,N'-di-t-butylethylenediamine and 26.35 g (260.9 mmol) of n-butyldimethylamine are separately dissolved in 2,300 g of methanol To obtain a mixed solution. When aeration and stirring were carried out using a nitrogen-air mixture having an 8% oxygen concentration at a flow rate of 5.2 L/min, the mixed solution was dropwise added to the mixture in the reactor over 230 minutes. After the addition was completed, 1,500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirring mixture to terminate the reaction. The aqueous layer and the organic layer are separated. Subsequently, the organic layer was washed with a 1N aqueous solution of hydrochloric acid and then washed with purified water. The solution thus obtained was concentrated to 50% by weight using an evaporator to obtain a toluene solution of 1,981 g of a difunctional phenylene ether oligomer (resin "C"). The resin "C" had a number average molecular weight of 1,975, a weight average molecular weight of 3,514, and a hydroxyl equivalent of 990.

(Synthesis of vinyl compounds)

833.40 g of a resin "C" in toluene solution, 76.7 g of vinylbenzyl chloride (CMS-P), 1,600 g of dichloromethane, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of 30.5 wt% Aqueous NaOH solution was added to the reactor equipped with a stirrer, a thermometer and a reflux tube. The mixture was stirred at a reaction temperature of 40 °C. The mixture was stirred for 24 hours, and then the organic layer was washed with 1N aqueous hydrochloric acid and then washed with purified water. The solution thus obtained was concentrated using an evaporator. The concentrated solution was dropped into methanol to obtain a solid. The solid was recovered by filtration, and the solid was recovered by drying in vacuo to yield 450.1 g of the compound "D". The vinyl compound "D" has a number average molecular weight of 2,250, a weight average molecular weight of 3,920, and 1,189 g/vinyl. Vinyl equivalent.

(Synthesis Example 3) (Synthesis of difunctional phenylene ether oligomers)

13.1 g (0.12 mol) of CuCl, 707.0 g (5.5 mol) of di-n-butylamine and 4,000 g of methyl ethyl ketone were added to a longitudinally long reactor having a volume of 12 liters equipped with a stirrer, a thermometer, an air sample tube and a baffle. The mixture was stirred at a reaction temperature of 40 °C. When using 2 L/min of air for aeration and agitation, 410.2 g (1.6 mol) of 4,4'-methylenebis(2,6-dimethylphenol) and 586.5 g (4.8 mol) 2 were used. A solution of 6-dimethylphenol in 8,000 g of methyl ethyl ketone was added dropwise to the mixture in the reactor over 120 minutes. An aqueous solution of disodium edetate dihydrogen dihydrogen was added to the stirred mixture to terminate the reaction. Subsequently, washing was performed three times with a 1 N aqueous hydrochloric acid solution and then with ion-exchanged water. The solution thus obtained was concentrated using an evaporator and then dried under reduced pressure to obtain 946.6 g of a bifunctional phenylene ether oligomer (resin "E"). The resin "E" had a number average molecular weight of 801, a weight average molecular weight of 1,081, and a hydroxyl equivalent of 455.

(Synthesis of vinyl compounds)

480.0 g of resin "E", 260.2 g of vinylbenzyl chloride (CMS-P), 2,000 g of tetrahydrofuran, 240.1 g of potassium carbonate and 60.0 g of 18-crown-6-ether were added to a mixer equipped with a stirrer, a thermometer and a reflux tube. reactor. The mixture was stirred at a reaction temperature of 30 °C. Stirring was carried out for 6 hours. Subsequently, the mixture was concentrated with an evaporator, diluted with 2,000 g of toluene and then washed with water. The organic layer was concentrated and then dropped into methanol to obtain a solid. The solid was recovered by filtration and dried in vacuo to recover a solid. 392.2 g of vinyl compound "F". The vinyl compound "F" had a number average molecular weight of 988, a weight average molecular weight of 1,420, and a vinyl equivalent of 558 g/vinyl group.

(Synthesis Example 4) (Synthesis of difunctional phenylene ether oligomers)

13.1 g (0.12 mol) of CuCl, 707.0 g (5.5 mol) of di-n-butylamine and 4,000 g of methyl ethyl ketone were placed in a longitudinally long reactor having a volume of 12 liters equipped with a stirrer, a thermometer, an air sample tube and a baffle. The mixture was stirred at a reaction temperature of 40 °C. When using 2 L/min of air for aeration and agitation, 82.1 g (0.32 mol) of 4,4'-methylenebis(2,6-dimethylphenol) and 586.5 g (4.8 mol) 2, A solution of 6-dimethylphenol in 8,000 g of methyl ethyl ketone was added dropwise to the mixture in the reactor over 120 minutes. An aqueous solution of disodium edetate dihydrogen dihydrogen was added to the stirred mixture to terminate the reaction. Subsequently, washing was performed three times with a 1 N aqueous hydrochloric acid solution and then with ion-exchanged water. The solution thus obtained was concentrated using an evaporator and then dried under reduced pressure to obtain 632.5 g of a bifunctional phenylene ether oligomer (resin "G"). The resin "G" had a number average molecular weight of 1,884, a weight average molecular weight of 3,763, and a hydroxyl equivalent of 840.

(Synthesis of vinyl compounds)

480.0 g of resin "G", 140.5 g of vinylbenzyl chloride (CMS-P), 2,000 g of tetrahydrofuran, 129.6 g of potassium carbonate and 32.4 g of 18-crown-6-ether were added to a mixer equipped with a stirrer, a thermometer and a reflux tube. reactor. The mixture was stirred at a reaction temperature of 30 °C. Stirring was carried out for 6 hours. Subsequently, the mixture was concentrated with an evaporator, diluted with 2,000 g of toluene and connected. Wash with water. The organic layer was concentrated and then dropped into methanol to obtain a solid. The solid was recovered by filtration and dried in vacuo to yield 415.3 g of vinyl compound "H". The vinyl compound "H" had a number average molecular weight of 2,128, a weight average molecular weight of 4,021, and a vinyl equivalent of 1,205 g/vinyl group.

(Synthesis Example 5) (Synthesis of difunctional phenylene ether oligomers)

18.0 g (78.8 mmol) 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 0.172 g (0.77 mmol) CuBr ₂ , 0.199 g (1.15 mmol) N, N'-di third Ethylenediamine, 2.10 g (2.07 mmol) n-butyldimethylamine, 139 g methanol and 279 g toluene were added to a longitudinally long reactor with a volume of 2 liters equipped with a stirrer, thermometer, air sample tube and baffle . Separately, 48.17 g (0.394 mol) of 2,6-dimethylphenol, 0.245 g (1.44 mmol) of N,N'-di-t-butylethylenediamine and 2.628 g (25.9 mmol) of n-butyldimethylamine It was dissolved in 133 g of methanol and 266 g of toluene to obtain a mixed solution. When aeration was carried out using air at an air flow rate of 0.5 L/min, the mixed solution was dropwise added to the reactor over 132 minutes, wherein the mixture was stirred at a liquid temperature of 40 °C. After the completion of the addition of the mixed solution, the resulting mixture was further stirred for 120 minutes. Subsequently, 400 g of water in which 2.40 g of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirring mixture to terminate the reaction. The aqueous layer and the organic layer are separated. Subsequently, washing was carried out using pure water. The solution thus obtained was concentrated using an evaporator. The concentrated solution was dried in vacuum at 120 ° C for 3 hours to obtain 54.8 g of a bifunctional phenylene ether oligomer (resin "I"). The resin "I" had a number average molecular weight of 1,348, a weight average molecular weight of 3,267, and a hydroxyl equivalent of 503.

(Synthesis of vinyl compounds)

25.0 g of resin "I", 8.69 g of vinylbenzyl chloride (trade name: CMS-P; supplied by Seimi Chemical Co., Ltd.) and 100.0 g of dimethylformamide were added to the mixer equipped with a stirrer. A 1 L separable flask with a reflux tube and a dropping funnel. When the mixture was stirred under heating at 50 ° C, 10.91 g of 28% by weight sodium methoxide (methanol solution) was added dropwise from the dropping funnel over 20 minutes. After the dropwise addition was completed, the resulting mixture was further stirred at 50 ° C for 1 hour. 1.99 g of 28% by weight sodium methoxide (methanol solution) was charged to the reactor, and the resulting mixture was heated to 60 ° C and stirred for 3 hours. Separately, 1.11 g of 85 wt% phosphoric acid was added to the reactor. The resulting mixture was stirred for 10 minutes and then cooled to 40 °C. The reaction mixture was dropped into 150 g of pure water to obtain a solid. The solid was recovered by suction filtration. The solid was then washed twice with 200 g of purified water and three times with 200 g of methanol. The washed solid was dried in vacuum at 60 ° C for 30 hours to obtain 28.25 g of a vinyl compound "J". The vinyl compound "J" had a number average molecular weight of 1,435, a weight average molecular weight of 3,158, and a vinyl equivalent of 612 g/vinyl group.

(Synthesis Example 6) (Synthesis of difunctional phenylene ether oligomers)

3.88 g (17.4 mmol) of CuBr ₂ , 0.75 g (4.4 mmol) of N,N'-di-t-butylethylenediamine, 28.04 g (277.6 mmol) of n-butyldimethylamine and 2,600 g of toluene were added to have 12 liters A longitudinally long reactor of volume and equipped with a stirrer, thermometer, air sample tube and baffle. The mixture was stirred at a reaction temperature of 40 °C. 129.3 g (0.48 mol) of 2, 2',3,3',5,5'-hexamethyl-(1,1'-diphenyl)-4,4'-diol, 233.7 g (1.92 mol) 2,6-Dimethylphenol, 64.9 g (0.48 mol) of 2,3,6-trimethylphenol, 0.51 g (2.9 mmol) of N,N'-di-t-butylethylenediamine and 10.90 g ( 108.0 mmol) n-butyldimethylamine was separately dissolved in 2,300 g of methanol to obtain a mixed solution. When aeration and stirring were carried out using a nitrogen-air mixture having a 3% oxygen concentration at a flow rate of 5.2 L/min, the mixed solution was dropwise added to the mixture in the reactor over 230 minutes. After the addition was completed, 1,500 g of water in which 19.89 g (52.3 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirring mixture to terminate the reaction. The aqueous layer and the organic layer are separated. Subsequently, the organic layer was washed with a 1N aqueous solution of hydrochloric acid and then washed with purified water. The solution thus obtained was concentrated to 50% by weight using an evaporator to obtain a toluene solution of 836.5 g of a bifunctional phenylene ether oligomer (resin "K"). The resin "K" had a number average molecular weight of 986, a weight average molecular weight of 1,530, and a hydroxyl equivalent of 471.

(Synthesis of vinyl compounds)

836.5 g of a resin "K" in toluene solution, 162.6 g of vinylbenzyl chloride (trade name: CMS-P; supplied by Seimi Chemical Co., Ltd.), 1,600 g of dichloromethane, 12.95 g of benzyl dimethyl Amine, 420 g of pure water and 178.0 g of a 30.5 wt% aqueous NaOH solution were charged to a reactor equipped with a stirrer, a thermometer and a reflux tube. The mixture was stirred at a reaction temperature of 40 °C. Stirring was carried out for 24 hours. The organic layer was then washed with a 1N aqueous solution of hydrochloric acid and then washed with purified water. The solution thus obtained was concentrated using an evaporator, and the concentrated solution was dropped into methanol to obtain a solid. Filtered back The solid was taken up and dried to recover the solid in vacuo to give 503.5 g of the vinyl compound "L". The vinyl compound "L" had a number average molecular weight of 1,187, a weight average molecular weight of 1,675, and a vinyl equivalent of 590 g/vinyl group.

(Synthesis Comparative Example 1) (Synthesis of a vinyl benzyl ether compound of a naphthol aralkyl resin)

40 g (hydroxyl 0.194 mol) naphthol aralkyl resin (SN475, supplied by Nippon Steel Chemical Co., Ltd.), 37.0 g (0.233 mol) vinyl benzyl chloride (trade name CMS-P; A 1 L round reactor equipped with a magnetic stirrer, a Dairy condenser, a thermometer and a dropping funnel was placed in a solution of 200 g of dimethylformamide supplied by Seimi Chemical Co., Ltd. The gas in the reactor was replaced with nitrogen. Subsequently, the mixture was stirred at a reaction temperature of 50 °C. 46.2 g (0.23 mol of sodium methoxide) and 28.4% by weight of sodium methoxide in methanol were placed in a dropping funnel. A solution of sodium methoxide in methanol was added to the reactor over 30 minutes. The resulting mixture was stirred at 50 ° C for 1 hour. An additional 3.9 g (0.01 mol of sodium methoxide) of 28.4 wt% sodium methoxide in methanol was added dropwise to the reactor. After the dropwise addition was completed, the mixture was stirred at 60 ° C for 4.5 hours to allow the mixture to react. 2.3 g (0.021 mol) of an 85% by weight aqueous phosphoric acid solution was added dropwise, and the mixture was stirred for 10 minutes. It was confirmed that the pH was 7. The resulting salt was removed by suction filtration. Subsequently, the reaction mixture was dropped into 2,500 g of methanol over 5 minutes to obtain a solid. The solid was recovered by suction filtration. Subsequently, the solid was dried using a vacuum dryer at 50 ° C for 10 hours to obtain 38.4 g of a vinyl compound "M". The solid was subjected to IR analysis and NMR (nuclear magnetic resonance) analysis. The disappearance of the absorption peak of the phenolic hydroxyl group (3600 cm ^-1 ) in the IR analysis and the appearance of a peak derived from vinylbenzyl ether (4.6-5.8 ppm) in the NMR analysis confirmed the conversion of the functional group. The polyvinyl compound "M" was measured by gel permeation chromatography (GPC), and as a result, the polyvinyl compound "M" had a number average molecular weight of 658, a weight average molecular weight of 4,534, and a vinyl equivalent of 325 g/vinyl group. .

(Examples 1 to 9 and Comparative Examples 1 to 8)

The vinyl compounds "B", "D", "F" obtained in Synthesis Examples 1, 2, 3, 4, 5, 6 and Synthesis Comparative Example 1 in accordance with the weight ratios shown in Table 1 or Table 2 were obtained. One of "H", "J", "L" and "M" and the maleidin compound are placed in a separable flask with a stirrer. N,N-dimethylacetamide was added to the mixture to give the mixture a solid content concentration of 20% by weight. The mixture was heated to 60 ° C and stirred for 1 hour to prepare a solution of the curable resin composition. The solution was coated on a shiny surface of a 18-μm electrolytic copper foil (3EC-III, supplied by Mitsui Mining and Smelting Co., Ltd.) with a doctor blade (with a gap of 200 μm). The coating solution was air-dried at room temperature for 10 minutes and then dried at 50 ° C for 20 minutes using an air blow dryer to obtain a curable resin composition of an additional base material having a resin layer thickness of about 15 μm. Subsequently, the curable resin composition of the additional base material was heated in air at 200 ° C for 30 minutes using an air blow dryer to obtain a cured product of the additional base material. Subsequently, a copper foil as a base material is removed by etching to obtain a film. The film has a thickness of about 15 μm. The glass transition temperature, dielectric constant, dielectric loss tangent, mechanical properties and chemical resistance of the film were measured and evaluated. Tables 1 and 2 show the results.

BMI-80: 2, 2'-bis[4-(4-maleimidophenoxy)phenyl]propane (supplied by KI KASEI KK, maleic imine equivalent: 285 g/malay) Imino group).

BMI-2300: a polycondensate of aniline, formaldehyde and maleic anhydride (supplied by Daiwakasei Industry Co., Ltd., maleimide equivalent: 179 g/maleimido).

BMI-7000: 4-methyl-1, 3-phenylene bismaleimide (supplied by Daiwakasei Industry Co., Ltd., maleimine equivalent: 141 g/maleimide group ).

The "unmeasurable" in Table 2 means that the sample for measurement cannot be prepared because the hardened material is brittle.

From Examples 1 to 7 and Comparative Examples 1 to 8, it was found that the resulting resin composition can be hardened in the presence of oxygen due to the combination of a vinyl compound having a phenylene ether structure and a maleic imine compound having a specific structure. And it can also produce hardened materials with high heat resistance, low dielectric properties, excellent mechanical properties and excellent chemical resistance.

(Examples 10-13, Comparative Example 9)

The vinyl compound "B", the maleimide compound, and the styrene-based thermoplastic elastomer obtained in Synthesis Example 1 in the weight ratio shown in Table 3 were placed in a separable flask equipped with a stirrer. Toluene was added to the mixture to give the mixture a solid content concentration of 20% by weight. The resulting mixture was heated to 60 ° C and stirred for 1 hour to prepare a solution of the curable resin composition. The solution was coated on a film of ethylene tetrafluoroethylene copolymer (ETFE) having a thickness of 50 μm with a doctor blade (with a gap of 200 μm). The coating solution was air-dried at room temperature for 10 minutes, and then dried at 50 ° C for 20 minutes using an air blow dryer to obtain a curable resin composition of an additional base material having a resin layer thickness of about 15 μm. Subsequently, the curable resin composition of the additional base material was heated in air at 200 ° C for 30 minutes using an air blow dryer to obtain a cured product of the additional base material. Subsequently, the ETFE film as a base material was peeled off by hand to obtain a film. The glass transition temperature, dielectric constant, dielectric loss tangent, mechanical properties and chemical resistance of the film were measured and evaluated. Table 3 shows the results.

BMI-70: 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (supplied by KI KASEI KK, maleimine Equivalent: 221 g/maleimide).

BMI-TMH: 1,6-Bismaleimide-(2, 2, 4-trimethyl)hexane (available from Daiwakasei Industry Co., Ltd., maleimine equivalent: 159 g/ Maleidinium).

S8007L: hydrogenated styrene butadiene styrene copolymer (SEBS) (available from KURARAY Co., Ltd., having a weight average molecular weight of about 100,000 and a styrene content of 30% by weight).

From Examples 10 to 13 and Comparative Example 9, it was found that a vinyl compound having a phenylene ether structure and a maleate having a specific structure were imidized. Further, in combination with a styrenic thermoplastic elastomer, the resulting resin composition can be hardened in the presence of oxygen, and can also produce a cured product having low dielectric properties, high heat resistance, excellent mechanical properties, and excellent chemical resistance.

(Examples 14 to 15 and Comparative Examples 10 to 11)

The vinyl compound "D", the maleinimide compound and the styrene-based thermoplastic elastomer obtained in Synthesis Example 2 in the weight ratio shown in Table 4 were placed in a separable flask equipped with a stirrer. Toluene was added to the mixture to give the mixture a solid content concentration of 20% by weight. The resulting mixture was heated to 60 ° C and stirred for 1 hour to prepare a solution of the curable resin composition. The solution was coated on a film of ethylene tetrafluoroethylene copolymer (ETFE) having a thickness of 50 μm with a doctor blade (with a gap of 200 μm). The coating solution was air-dried at room temperature for 10 minutes, and then dried at 50 ° C for 20 minutes using an air blow dryer to obtain a curable resin composition of an additional base material having a resin layer thickness of about 15 μm. Subsequently, the curable resin composition of the additional base material was heated in an inert oven at 150 ° C for 2 hours or at 200 ° C for 30 minutes to obtain a cured product of the additional base material. Subsequently, the ETFE film was peeled off by hand to obtain a film. The glass transition temperature, dielectric constant, dielectric loss tangent, mechanical properties and chemical resistance of the film were measured and evaluated. Table 4 shows the results.

It is found from Table 4 that the resulting resin composition can be hardened at a low temperature due to the incorporation of a maleic imine compound, and can also produce a cured product having low dielectric properties, high heat resistance, excellent mechanical properties, and excellent chemical resistance. .

(Examples 16 to 19 and Comparative Example 12)

The vinyl compound "B" obtained in Synthesis Example 1 shown in Table 5 and/or the vinyl compound "F" obtained in Synthesis Example 3, the maleimide compound, and the styrene thermoplastic The elastomer was placed in a separable flask equipped with a stirrer. Tetrahydrofuran was added to the mixture to give the mixture a solid content concentration of 20% by weight. The resulting mixture was heated to 60 ° C and stirred for 1 hour to prepare a solution of the curable resin composition. The solution was applied to a 18-μm electrolytic copper foil (3EC-III by a scraper (with a gap of 200 μm) by Mitsui Mining and Smelting Co., Ltd. Provided on the shiny surface. The coating solution was air-dried at room temperature for 10 minutes, and then dried at 50 ° C for 20 minutes using an air blow dryer to obtain a curable resin composition of an additional base material having a resin layer thickness of about 15 μm. Subsequently, the curable resin composition of the additional base material was heated in air at 150 ° C for 2 hours using an air blow dryer to obtain a cured product of the additional base material. Subsequently, the copper foil as a base material is removed by etching to obtain a film. The glass transition temperature, dielectric constant, dielectric loss tangent, mechanical properties and chemical resistance of the film were measured and evaluated. Table 5 shows the results.

From Examples 16 to 19 and Comparative Example 12, it was found that the resulting resin composition can be obtained by combining a vinyl compound having a phenylene ether structure, a maleimide compound having a specific structure, and a styrenic thermoplastic elastomer. It hardens at a low temperature in the presence of oxygen, and can also produce a cured product having low dielectric properties, high heat resistance, excellent mechanical properties, and excellent chemical resistance.

(Formation 20 enhancement layer formation)

A toluene solution (resin solid content: 20% by weight) of the same curable resin composition as the toluene solution of the curable resin composition prepared in Example 10 was applied to an 18-μm electrolytic copper foil by a doctor blade (with a gap of 400 μm). (3EC-III) on the rough surface. The coating solution was air-dried at room temperature for 10 minutes, and then dried at 80 ° C for 20 minutes using an air blow dryer to obtain a curable resin composition of an additional base material each having a resin layer thickness of about 40 μm. The curable resin composition of the additional base material is placed on a core material having a line/space=100 μm/100 μm pattern on both surfaces (EL190, copper foil thickness is 18 μm, On both surfaces of Mitsubishi Gas Chemical Co., Inc., a resin composition is applied to each surface. The resin composition was hardened under heating at 170 ° C and a pressure of 2 MPa for 2 hours to obtain a four-layered plate. The copper foil peeling strength of the outermost copper foil was 0.8 kN/m. Next, the copper foil is removed by etching. It was subsequently found that the inner layer pattern was covered and there were no voids.

(Example 21 production of multilayer board)

A toluene solution (resin solid content: 20% by weight) of the same curable resin composition as the toluene solution of the curable resin composition prepared in Example 11 was applied to a vinyl having a thickness of 50 μm by a doctor blade (with a gap of 400 μm). On a tetrafluoroethylene copolymer (ETFE) film. The coating solution was air dried at room temperature for 10 minutes, and then air blast at 50 ° C The dryer was dried for 20 minutes to obtain a curable resin composition of an additional base material having a resin layer thickness of about 50 μm. Subsequently, the ETFE film was peeled off from the curable resin composition of the additional base material by hand to obtain a hardenable film. The curable film is sandwiched between core materials having a line/space = 100 μm/100 μm pattern on one of the two surfaces (HL832, copper foil thickness 12 μm, supplied by Mitsubishi Gas Chemical Co., Inc.) to The patterned surface of the core material is in contact with the curable film. The hardened film was cured by heating at 170 ° C and a pressure of 2 MPa for 2 hours to bond the core materials to each other. The cross section was observed through a microscope. It was subsequently found that the inner layer pattern was covered and there were no voids.

(Examples 22 and 23)

The vinyl compound "B" obtained in Synthesis Example 1 shown in Table 6 was placed in a separable flask equipped with a stirrer, a maleimide compound, a styrenic thermoplastic elastomer, and a flame retardant. in. Tetrahydrofuran was added to the mixture to give the mixture a solid content concentration of 20% by weight. The resulting mixture was heated to 60 ° C and stirred for 1 hour to prepare a solution of the flame-retardant curable resin composition of Example 22. The vermiculite was added to the resin composition solution of Example 22, and these components were stirred and mixed to prepare a solution of the curable resin composition containing the inorganic filler of Example 23. The resin composition solution of Example 22 was coated on a shiny surface of 18-μm electrolytic copper foil (3EC-III, supplied by Mitsui Mining and Smelting Co., Ltd.) with a doctor blade (with a gap of 200 μm). The resin composition solution of Example 23 was coated on a shiny surface of an 18-μm electrolytic copper foil (3EC-III) with a doctor blade (with a gap of 200 μm). Coating of Example 22 at room temperature The solution and the coating solution of Example 23 were air-dried independently for 10 minutes and then dried at 80 ° C for 5 minutes using an air blow dryer to obtain a curable resin composition of an additional base material, respectively. The curable resin composition of each additional base material has a resin layer thickness of about 20 μm. Subsequently, the curable resin composition of these additional base materials was heated in air at 150 ° C for 2 hours using an air blow dryer to obtain a cured product of the additional base material, respectively. The copper foil as a base material is removed by etching to obtain a film, respectively. The glass transition temperature, dielectric constant, dielectric loss tangent, mechanical properties, chemical resistance, and flame retardancy of the film were measured and evaluated. Table 6 shows the results.

PX200: 1, 3-phenylenebis(2,6-di-xylenephosphonate) (supplied by Daihachi Chemical Industry Co., Ltd.).

SC2050: Fused vermiculite (ADMAFINE SC-2050: by Admatechs provide).

It was found from Example 22 that, since a vinyl compound having a phenylene ether structure, a maleic imide compound having a specific structure, a styrene-based thermoplastic elastomer, and a flame retardant are further combined, the obtained resin composition can be It cures at a low temperature in the presence of oxygen, and can also produce a cured product having low dielectric properties, high heat resistance, excellent mechanical properties, excellent chemical resistance, and flame retardancy. Further, it has been found that the resin composition obtained can be hardened at a low temperature in the presence of oxygen due to further incorporation of a filler, and can also have low dielectric properties, high heat resistance, excellent mechanical properties, excellent chemical resistance, and excellent flame retardancy. And a low thermal expansion hardened material.

Claims (16)

A curable resin composition comprising a mixture of a vinyl compound (a) represented by the formula (1) or at least two vinyl compounds (a) of the formula (1) different in structure from each other, and at least a maleic imine compound (b) selected from the group consisting of the maleidin compound (b) represented by the general formula (5) to the general formula (8), Wherein -(OXO)- represents a moiety of the formula (2) or the formula (3), -(YO)- represents an arrangement of the moiety of the formula (4) or a random arrangement of at least two moieties of the formula (4), And each of a and b is an integer from 0 to 100, but at least one of a and b is not 0. Wherein R ₁ , R ₂ , R ₃ , R ₇ and R ₈ are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R ₄ , R ₅ and R ₆ are The same or different and represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, Wherein R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or Phenyl, -A- represents a linear, branched or cyclic divalent hydrocarbon radical having 20 or fewer carbon atoms, Wherein R ₁₇ and R ₁₈ are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R ₁₉ and R ₂₀ are the same or different and represent a hydrogen atom, a halogen atom, An alkyl or phenyl group having 6 or fewer carbon atoms, Wherein R ₂₁ to R ₂₈ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, and B represents a single bond, a divalent hydrocarbon group having 20 or less carbon atoms or an oxygen atom, Wherein R ₂₉ to R ₃₆ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, and D represents a divalent hydrocarbon group having 20 or less carbon atoms. Wherein R ₃₇ to R ₄₇ are the same or different and represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, and c is an integer of 1 to 20, Wherein E represents a divalent aliphatic hydrocarbon group having 20 or less carbon atoms. The curable resin composition of claim 1, wherein in the vinyl compound (a), -(OXO)- is a part of the formula (9), the formula (10) or the formula (11) And -(YO)- is an arrangement of the parts of the formula (12) or the formula (13), or a random arrangement of the parts of the formula (12) and the formula (13), Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same or different and represent a hydrogen atom or a methyl group, and -A- represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. , Wherein -A- represents a linear, branched or cyclic divalent hydrocarbon group having 20 or fewer carbon atoms . The curable resin composition of claim 1, wherein the vinyl compound (a) has a number average molecular weight of 500 to 3,000 and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1 to 3. The curable resin composition of claim 1, wherein the vinyl group of the vinyl compound (a): the maleimide group of the maleimide compound (b) has a molar ratio of 1:0.1. To 1:5. The curable resin composition of claim 1, which further comprises a styrene thermoplastic elastomer (c). The curable resin composition of claim 1, which further comprises a flame retardant (d). The curable resin composition of claim 6, wherein the flame retardant (d) is a phosphorus flame retardant, and the content of phosphorus in the curable resin composition is from 0.1 to 5% by weight. The sclerosing resin composition of claim 7, wherein the phosphorus flame retardant is 1,3-phenylenebis(2,6-dixylphosphonic acid). The curable resin composition of claim 1, which further comprises a filler (e). The curable resin composition of claim 9, wherein the filler (e) is vermiculite, and the content of the vermiculite in the curable resin composition is from 10 to 70% by weight. A curable resin composition solution obtained by dissolving and dispersing a curable resin composition defined in claim 1 of the patent application in a solvent. a hardened material as defined in item 1 of the scope of the patent application The curable resin composition is obtained by hardening. A curable resin composition of an additional base material obtained by applying a curable resin composition as defined in claim 1 to a base material. A cured product of an additional base material obtained by hardening a curable resin composition of an additional base material as defined in claim 13 of the patent application. A curable film obtained by removing a base material from a curable resin composition of an additional base material defined in claim 13 of the patent application. A film obtained by curing a curable resin composition defined in the first application of the patent application in the form of a film.